WO2004043592A1 - Supported catalyst containing rhenium and method for hydrogenation of carbonyl compounds in liquid phase by means of said catalyst - Google Patents

Supported catalyst containing rhenium and method for hydrogenation of carbonyl compounds in liquid phase by means of said catalyst Download PDF

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Publication number
WO2004043592A1
WO2004043592A1 PCT/EP2003/012379 EP0312379W WO2004043592A1 WO 2004043592 A1 WO2004043592 A1 WO 2004043592A1 EP 0312379 W EP0312379 W EP 0312379W WO 2004043592 A1 WO2004043592 A1 WO 2004043592A1
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Prior art keywords
rhenium
catalyst
hydrogenation
periodic table
elements
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PCT/EP2003/012379
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German (de)
French (fr)
Inventor
Markus Schubert
Michael Hesse
Rolf-Hartmuth Fischer
Take Constantinescu
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Basf Aktiengesellschaft
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Priority to AU2003276258A priority Critical patent/AU2003276258A1/en
Priority to EP03810970A priority patent/EP1572354B1/en
Priority to US10/534,621 priority patent/US7214641B2/en
Priority to DE50303747T priority patent/DE50303747D1/en
Priority to JP2004550946A priority patent/JP4608318B2/en
Publication of WO2004043592A1 publication Critical patent/WO2004043592A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D307/08—Preparation of tetrahydrofuran
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/506—Method of making inorganic composition utilizing organic compound, except formic, acetic, or oxalic acid or salt thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/506—Method of making inorganic composition utilizing organic compound, except formic, acetic, or oxalic acid or salt thereof
    • Y10S502/512—Carboxylic acid or salt thereof other than formic, acetic, or oxalic acid

Definitions

  • the invention relates to a process for the hydrogenation of compounds containing carbonyl groups in the liquid phase over supported catalysts containing rhenium and which have at least one further active metal which is applied to the support together with the rhenium in the form of a bimetallic compound.
  • DE-A 100 09 817 describes a rhenium-containing supported catalyst in which activated carbon which is not pre-oxidatively pretreated is used as the support material.
  • the catalysts also contain other transition metals, in particular platinum metals, in order to increase the catalyst activity. Rhenium and the other transition metals are applied to the support in the form of separate or common solutions of their respective salts. The hydrogenations described give alcohols as the main product.
  • DE-A 2 519 817 catalysts which simultaneously contain elements of groups VII and VIII of the periodic table of the elements.
  • Supported catalysts containing rhenium and additionally having platinum or palladium are preferred. These catalysts have, in particular, rhenium and palladium, which are preferably applied simultaneously to the support in the course of the catalyst preparation according to the exemplary embodiments.
  • the activity of the supported palladium-rhenium catalysts in hydrogenations of compounds containing carbonyl groups to alcohols is so low that the simultaneous use of high pressures and high temperatures of 215 to 230 ° C. is necessary. Carrying out the hydrogenations at high pressures and high temperatures is not very economical due to high energy and material costs.
  • the corrosiveness of the carboxylic acid solutions in particular increases under these conditions.
  • GBL gamma-butyrolactone
  • THF tetrahydrofuran
  • a rhenium-containing supported catalyst for the hydrogenation of carbonyl compounds such as dicarboxylic acids and / or their derivatives, in particular maleic acid and / or succinic acid, their anhydrides and / or esters, in particular to mixtures of optionally substituted ⁇ -butyrolactone and tetrahydrofuran, which is characterized in that that rhenium and at least one other metal from groups VIII or Ib of the Periodic Table of the Elements, in particular ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt) , Copper (Cu), silver (Ag) or cobalt (Co) in the form of at least one bimetallic precursor compound was applied to the support.
  • carbonyl compounds such as dicarboxylic acids and / or their derivatives, in particular maleic acid and / or succinic acid, their anhydrides and / or esters, in particular to
  • a bimetallic precursor compound is understood to mean a compound which has both a rhenium atom or cation and also an atom or cation of this metal from groups VIII or Ib of the Periodic Table of the Elements.
  • Perrhenate double salts are preferred as the bimetallic precursor compound, particularly preferably those of the general formula I
  • Me for a metal from groups VIII and Ib of the Periodic Table of the Elements, in particular for Ru (ruthenium), Rh (rhodium), Pd (palladium), Os (osmium), Ir (iridium), Pt (platinum ), Cu (copper), Ni (nickel), Ag (silver) or Co (cobalt), a is 1 or 2, b is an integer from 1 to 8, c is an integer from 0 to 5, d 2, 3 or 4 and e represents an integer from 0 to 12. Double salts are mixed crystals of two salts. Anions and cations of an ion crystal can be replaced by other cations and anions without changing the crystal structure type.
  • Pd ( ⁇ H 3 ) 4 (ReO) 2 and / or Pt (NH 3 ) 4 (ReO 4 ) 2 is particularly preferably used as the bimetallic precursor compound.
  • carrier materials known for the production of hydrogenation catalysts are suitable as the carrier material.
  • Silicon oxide, aluminum oxide, titanium dioxide, silicon dioxide, magnesium oxide, optionally pretreated activated carbon, graphitic carbon carriers, nitrides, silicide, carbides or borides are preferred.
  • the pretreatment mentioned can be an oxidative pretreatment, as described for example in EP-A 848991.
  • Carriers of optionally pretreated activated carbon are preferably used.
  • Rhenium (Re, calculated as metal) and the further metal from Group VIII or Ib of the periodic table are in an amount of 0.03 to 30% by weight, preferably 1 to 12% by weight, particularly preferably 2 to 5% by weight .-%, based on the total catalyst from the carrier and active composition, applied.
  • the catalysts according to the invention are preferably, in particular, free of chromium.
  • the application of the active components rhenium and the other metal of group VIII or Ib of the periodic table of the elements can be done by impregnation in one or several steps with an aqueous, alcoholic or other organic solvent solution of the respective dissolved bimetallic precursor compound, particularly preferably the double salt of the general formula I, equilibrium adsorption in one or more steps of the bimetallic precursor compound dissolved in aqueous or alcoholic solution, particularly preferred of the double salt of the general formula I can be carried out on the carrier.
  • the active components will be applied simultaneously and evenly to the carrier material. There is a drying step between the individual impregnation and equilibrium adsorption steps to remove the solvent.
  • the active components are preferably applied in one step by impregnation with an aqueous salt solution.
  • the impregnated catalyst is dried to remove the solvent after the impregnation or equilibrium adsorption step.
  • the drying temperature is 30-350 ° C, preferably 40-280 ° C, particularly preferably 50-150 ° C.
  • the active components are particularly evenly distributed on the support of the catalyst according to the invention; in particular, the intensity ratio of rhenium to metal (Me) of Group VIII or Ib of the Periodic Table of the Elements shows less than fluctuations over more than 99.9% of the analyzed points over the entire catalyst particles the factor 10, based on the statistical mean, preferably fluctuations smaller than factor 5 in 98% of the analyzed points on the catalyst surface and particularly preferably fluctuations smaller than factor 2 in 80% of the analyzed points.
  • Me rhenium to metal
  • This factor was determined using SEM-EDX (Scanning electron microscope-energy dispersive x-ray spectroscopy). The method is known per se and, for example, in Ulmann's Encyclopedia of Industrial Chemistry 6 th Edition 2000 Electronic Release wrote loading.
  • the catalysts are usually activated before they are used. This activation can be done by applying a reducing gas atmosphere to the catalyst. Activation with the aid of hydrogen is preferably used.
  • the activation temperature is usually 100-500 ° C., preferably 130-400 ° C., particularly preferably 150-400 ° C.
  • Alternative reduction methods are the reduction of the metallic components by bringing them into contact with a liquid reducing agent such as hydrazine, formaldehyde or sodium formate.
  • the liquid reducing agents are usually at temperatures between 10 and 100 ° C. brought into contact. Contacting at temperatures between 20 to 80 ° C. is particularly preferred.
  • the hydrogenation is usually carried out at 110-250 ° C., preferably at 150-250 ° C. Hydrogenation is usually carried out at a reaction pressure between 5 and 220 bar, preferably 40 and 150 bar. The hydrogenation is preferably carried out in the liquid phase in a fixed bed.
  • Suitable starting materials for the hydrogenation are generally carbonyl compounds, which can additionally contain double or triple C-C bonds.
  • aldehydes are propionaldehyde, butyraldehyde, crotonaldehyde, ethylhexanal, nonanal and glucose.
  • carboxylic acids are succinic acid, fumaric acid, maleic acid.
  • esters are esters of the aforementioned acids, e.g. as methyl, ethyl, propyl or butyl esters, lactones, e.g. gamma-butyrolactone, delta-valerolactone or caprolactone can be used.
  • Anhydrides such as succinic anhydride or maleic anhydride can also be used.
  • Preferred starting materials are C -dicarboxylic acids and / or their derivatives, particularly preferably succinic acid, maleic acid, succinic anhydride, maleic anhydride and the esters of these acids.
  • Mixtures of aldehydes, carboxylic acids, esters, anhydrides and / or lactones, preferably mixtures of carboxylic acids, can of course also be used.
  • the compounds to be hydrogenated can be hydrogenated in bulk or in solution.
  • a suitable solvent is e.g. one of the hydrogenation products itself, or substances such as alcohols such as methanol, ethanol, propanol or butanol are used, and ethers such as THF or ethylene glycol ether or gamma-butyrolactone are also suitable.
  • a preferred solvent is water, especially in the hydrogenation of carboxylic acids.
  • the hydrogenation can be carried out in the liquid phase, in one or more stages. In the liquid phase, both the suspension and the fixed bed procedure are possible. In exothermic reactions, the heat can be dissipated by external coolants (e.g. tubular reactor). Boiling cooling in the reactor is also possible, especially if hydrogenation is carried out without recycling the product. A cooler in the return flow is recommended for product return.
  • external coolants e.g. tubular reactor
  • the intensities (corresponding to the contents) of the rhenium and the palladium were determined using a Philips ESEM-XL30-FG SEM-EDX spectrometer with EDX probe. The analysis voltage was 30 KV. The particles were divided in preparation so that a clean cut surface was obtained. From this cut surface, more than 300 ⁇ m in steps of 15 ⁇ m were examined with SEM-EDX for their Pd and Re content. A ratio of the intensities of Pd and Re can be calculated at each measuring point.
  • the catalyst contained 0.5 wt% Pd and 2 wt% Re.
  • Example 4 1.11 g of the Pd-Re salt were dissolved in 130 g of water at 40.degree. 10 g of this solution were applied to 30 g of the activated carbon carrier (Degussa 180) with stirring. Then the catalyst was dried at 120 ° C. for 1 h. After a washing step with water, the soaking and drying procedure was repeated until all of the solution had been applied to the support. The catalyst was then dried and reduced as in Example 2. The catalyst contained 0.5 wt% Pd and 2 wt% Re. Example 4
  • succinic anhydride (BSA), which was metered in at 6.06 g / h as a 20% strength by weight solution in gamma-butyrolactone, was hydrogenated at 235 ° C. and 40 bar in continuous operation.
  • the molar ratio H 2 : BSA was 35.
  • a conversion of 91% a product yield of 81% (39% tetrahydrofuran (THF) and 35% ⁇ -butyrolactone) was achieved.

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  • Engineering & Computer Science (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to a method for hydrogenation of carbonyl compounds, in particular C4-dicarboxylic acids for producing mixtures of tetrahydrofuranne and gamma-butyrolactone on supported rhenium-containing catalysts. Said catalysts are characterised in that rhenium and at least another metal of groups VIII or Ib of the Periodic table of elements, in particular ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt), copper (Cu), silver (Ag) or cobalt (Co) in the form of at least one bimetallic precursor compound are applied to the support. The inventive catalysts are also disclosed.

Description

RHENIUMHALTIGER TRÄGERKATALYSATOR UND VERFAHREN ZUR HYDRIERUNG VON CARBONYLVERBINDUNGEN IN FLÜSSIGER PHASE UNTER VERWENDUNG DES KATALYSATORSRHENIUM-CONTAINING CARRIER CATALYST AND METHOD FOR HYDROGENATING CARBONYL COMPOUNDS IN LIQUID PHASE USING THE CATALYST
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Hydrierung von Carbonylgruppen enthaltenden Verbindungen in der Flüssigphase an rheniumhaltigen Trägerkatalysatoren, die mindestens ein weiteres Aktivmetall aufweisen, das zusammen mit dem Rhenium in Form einer bimetallischen Verbindung auf den Träger aufgebracht wird.The invention relates to a process for the hydrogenation of compounds containing carbonyl groups in the liquid phase over supported catalysts containing rhenium and which have at least one further active metal which is applied to the support together with the rhenium in the form of a bimetallic compound.
Die industrielle Hydrierung von Carbonylgruppen enthaltenden Verbindungen wie Aldehyden, Ketonen, Carbonsäuren, Carbonsäureanhydriden mit Wasserstoff an rheniumhaltigen Katalysatoren ist seit langem bekannt.The industrial hydrogenation of compounds containing carbonyl groups, such as aldehydes, ketones, carboxylic acids, carboxylic acid anhydrides, with hydrogen over rhenium-containing catalysts has been known for a long time.
So beschreibt DE-A 100 09 817 einen rheniumhaltigen Trägerkatalysator, bei dem als Trägermaterial nichtoxidativ vorgehandelte Aktivkohle verwendet wird. Die Katalysatoren enthalten zudem weitere Übergangsmetalle, insbesondere Platinmetalle, um die Katalysatoraktivität zu steigern. Rhenium und die weiteren Übergangsmetalle werden dabei auf den Träger in Form getrennter oder gemeinsamer Lösungen ihrer jeweiligen Salze aufgebracht. Die beschriebenen Hydrierungen ergeben als Hauptprodukt Alkohole.For example, DE-A 100 09 817 describes a rhenium-containing supported catalyst in which activated carbon which is not pre-oxidatively pretreated is used as the support material. The catalysts also contain other transition metals, in particular platinum metals, in order to increase the catalyst activity. Rhenium and the other transition metals are applied to the support in the form of separate or common solutions of their respective salts. The hydrogenations described give alcohols as the main product.
Aus DE-A 2 519 817 sind Katalysatoren bekannt, die gleichzeitig Elemente der Gruppe VII und VIII des Periodensystems der Elemente enthalten. Bevorzugt sind rheniumhal- tige, zusätzlich Platin oder Palladium aufweisende Trägerkatalysatoren. Diese Katalysatoren weisen insbesondere Rhenium und Palladium auf, die im Verlauf der Katalysatorherstellung gemäß den Ausführungsbeispielen bevorzugt, gleichzeitig auf den Träger aufgebracht werden. Es ist gemäß der Offenbarung der DE-A 2 519 817 auch möglich die Palladiumverbindung zuerst auf den Träger aufzubringen. Die Aktivität der geträgerten Palladium-Rhenium-Katalysatoren in Hydrierungen von Carbonylgruppen enthaltender Verbindung zu Alkoholen ist so gering, dass die gleichzeitige Anwendung von hohen Drücken und hohen Temperaturen von 215 bis 230°C erforderlich wird. Die Durchführung der Hydrierungen bei hohen Drücken und hohen Temperaturen ist bedingt durch hohe Energie- und Materialkosten wenig wirtschaftlich. Zudem nimmt die Korrosität insbesondere der Carbonsäure-Lösungen unter diesen Bedingungen zu.DE-A 2 519 817 catalysts are known which simultaneously contain elements of groups VII and VIII of the periodic table of the elements. Supported catalysts containing rhenium and additionally having platinum or palladium are preferred. These catalysts have, in particular, rhenium and palladium, which are preferably applied simultaneously to the support in the course of the catalyst preparation according to the exemplary embodiments. According to the disclosure of DE-A 2 519 817, it is also possible to apply the palladium compound to the support first. The activity of the supported palladium-rhenium catalysts in hydrogenations of compounds containing carbonyl groups to alcohols is so low that the simultaneous use of high pressures and high temperatures of 215 to 230 ° C. is necessary. Carrying out the hydrogenations at high pressures and high temperatures is not very economical due to high energy and material costs. In addition, the corrosiveness of the carboxylic acid solutions in particular increases under these conditions.
Aus EP-A 1 112 776 ist ein Verfahren zur Hydrierung von C -Dicarbonsäuren, deren Anhydriden oder Estern unter Verwendung eines Katalysators bekannt, bei dem die Rheniumkomponente sehr gleichmäßig auf dem Trägermaterial verteilt ist. Die zusätz- lieh vorhandene Palladium-komponente zeigt jedoch ein deutliches Schalenprofil, so dass der Synergieeffekt, der vermutlich auf Bildung einer intermetallischen Phase besteht, nur begrenzt ausgenutzt wird. Mit den beschriebenen Katalysatoren wird gam- ma-Butyrolacton mit guter Selektivität gebildet. Die Produktgemische enthalten jedoch nur Spuren von THF.From EP-A 1 112 776 a process for the hydrogenation of C -dicarboxylic acids, their anhydrides or esters using a catalyst is known in which the rhenium component is distributed very uniformly on the support material. The additional loaned palladium component, however, shows a clear shell profile, see above that the synergy effect, which presumably consists in the formation of an intermetallic phase, is only used to a limited extent. Gamma-butyrolactone is formed with good selectivity using the catalysts described. However, the product mixtures only contain traces of THF.
Es ist die Aufgabe der vorliegenden Erfindung einen Katalysator für die Hydrierung von Carbonylverbindungen sowie ein Verfahren zur Hydrierung von Carbonylverbindungen, insbesondere Dicarbonsäuren wie Maleinsäure und/oder Bernsteinsäure oder deren Anhydriden oder Estern unter Verwendung dieses Katalysators zur Verfügung zu stel- len, mit dem insbesondere Gemische mit etwa gleichen Anteilen von gegebenenfalls substituiertes gamma-Butyrolacton (in folgenden „GBL") und Tetrahydrofuran (im folgenden „THF") herstellbar sind und dass es gestattet diese Gemische bei gutem Umsatz mit guter Gesamtselektivität herzustellen.It is the object of the present invention to provide a catalyst for the hydrogenation of carbonyl compounds and a process for the hydrogenation of carbonyl compounds, in particular dicarboxylic acids such as maleic acid and / or succinic acid or their anhydrides or esters, using this catalyst, with which in particular mixtures with approximately equal proportions of optionally substituted gamma-butyrolactone (hereinafter "GBL") and tetrahydrofuran (hereinafter "THF") can be prepared and that it allows these mixtures to be produced with good conversion and good overall selectivity.
Die Aufgabe wird gelöst durch einen rheniumhaltigen Trägerkatalysator zur Hydrierung von Carbonylverbindungen wie Dicarbonsäuren und/oder deren Derivaten, insbesondere von Maleinsäure und/oder Bersteinsäure, deren Anhydriden und/oder Estern insbesondere zu Gemischen von gegebenenfalls substituierten γ-Butyrolacton und Tetrahydrofuran, der dadurch gekennzeichnet ist, dass Rhenium und mindestens ein weite- res Metall der Gruppen VIII oder Ib des Periodensystems der Elemente, insbesondere Ruthenium (Ru), Rhodium (Rh), Palladium (Pd), Osmium (Os), Iridium (Ir), Platin (Pt), Kupfer (Cu), Silber (Ag) oder Cobalt (Co) in Form mindestens einer bimetallischen Vorläuferverbindung auf den Träger aufgebracht wurde.The object is achieved by a rhenium-containing supported catalyst for the hydrogenation of carbonyl compounds such as dicarboxylic acids and / or their derivatives, in particular maleic acid and / or succinic acid, their anhydrides and / or esters, in particular to mixtures of optionally substituted γ-butyrolactone and tetrahydrofuran, which is characterized in that that rhenium and at least one other metal from groups VIII or Ib of the Periodic Table of the Elements, in particular ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt) , Copper (Cu), silver (Ag) or cobalt (Co) in the form of at least one bimetallic precursor compound was applied to the support.
Unter einer bimetallischen Vorläuferverbindung wird dabei eine Verbindung verstanden, die sowohl ein Rheniumatom bzw. -kation als auch Atom bzw. Kation dieses Metalls der Gruppen VIII oder Ib des Periodensystems der Elemente aufweist.A bimetallic precursor compound is understood to mean a compound which has both a rhenium atom or cation and also an atom or cation of this metal from groups VIII or Ib of the Periodic Table of the Elements.
Bevorzugt werden als bimetallische Vorläuferverbindung Perrhenat-Doppelsalze, be- sonders bevorzugt solche der allgemeinen Formel IPerrhenate double salts are preferred as the bimetallic precursor compound, particularly preferably those of the general formula I
[Mea (NH3)b (OH)d (ReO4)d • eH2O (I)[Me a (NH 3 ) b (OH) d (ReO 4 ) d • eH 2 O (I)
oder deren Gemische eingesetzt, wobei Me für ein Metall der Gruppen VIII und Ib des Periodensystems der Elemente, insbesondere für Ru (Ruthenium), Rh (Rhodium), Pd (Palladium), Os (Osmium), Ir (Iridium), Pt (Platin), Cu (Kupfer), Ni (Nickel), Ag (Silber) oder Co (Cobalt) steht, a 1 oder 2 bedeutet, b eine ganze Zahl von 1 bis 8, c eine ganze Zahl von 0 bis 5, d 2, 3 oder 4 und e eine ganze Zahl von 0 bis 12 darstellt. Doppelsalze sind Mischkristalle zweier Salze. Anionen- und Kationen eines lo- nenkristalls können durch andere Kationen und Anionen ersetzt werden, ohne dass sich der Kristallstrukturtyp ändert. Ist das sich gegenseitig vertretende lonenpaar nicht rein statisch, sondern nach einem bestimmten Verteilungsplan im lonengitter angeord- net, resultiert ein Doppelsalz. Die Herstellung solcher Doppelsalze ist an sich bekannt und beispielsweise von Pechenyuk, S.I., Kuznetsov, VN., Popova, R.A., Zalkind, O.A., Zh. Νeorg. Khim. 24 (1979) 3306 beschrieben.or mixtures thereof, where Me for a metal from groups VIII and Ib of the Periodic Table of the Elements, in particular for Ru (ruthenium), Rh (rhodium), Pd (palladium), Os (osmium), Ir (iridium), Pt (platinum ), Cu (copper), Ni (nickel), Ag (silver) or Co (cobalt), a is 1 or 2, b is an integer from 1 to 8, c is an integer from 0 to 5, d 2, 3 or 4 and e represents an integer from 0 to 12. Double salts are mixed crystals of two salts. Anions and cations of an ion crystal can be replaced by other cations and anions without changing the crystal structure type. If the mutually representative ion pair is not purely static, but is arranged in the ion grid according to a certain distribution plan, a double salt results. The production of such double salts is known per se and, for example, from Pechenyuk, SI, Kuznetsov, VN., Popova, RA, Zalkind, OA, Zh. Νeorg. Khim. 24 (1979) 3306.
Erfindungsgemäß wurde erkannt, dass durch Einsatz dieser Doppelsalze zur Aufbrin- gung der katalytisch aktiven Komponenten auf den Träger eine gleichförmige Verteilung aller katalytisch aktiven Metalle erreicht wird.According to the invention, it was recognized that by using these double salts to apply the catalytically active components to the support, a uniform distribution of all catalytically active metals is achieved.
Besonders bevorzugt wird als bimetallische Vorläuferverbindung Pd (ΝH3)4 (ReO )2 und/oder Pt (NH3)4 (ReO4)2 verwendet.Pd (ΝH 3 ) 4 (ReO) 2 and / or Pt (NH 3 ) 4 (ReO 4 ) 2 is particularly preferably used as the bimetallic precursor compound.
Als Trägermaterial kommen alle für die Herstellung von Hydrierkatalysatoren bekannten Trägermaterialien in Frage. Bevorzugt werden Siliziumoxid, Aluminiumoxid, Titandioxid, Zikondioxid, Magnesiumoxid, gegebenenfalls vorbehandelter Aktivkohle, graphitischen Kohleträgern, Nitride, Silicid, Carbide oder Boride. Bei der erwähnten Vorbehandlung kann es sich um eine oxidative Vorbehandlung, wie sie beispielsweise in EP-A 848991 beschrieben ist, handeln. Bevorzugt werden Träger aus gegebenenfalls vorbehandelter Aktivkohle eingesetzt.All carrier materials known for the production of hydrogenation catalysts are suitable as the carrier material. Silicon oxide, aluminum oxide, titanium dioxide, silicon dioxide, magnesium oxide, optionally pretreated activated carbon, graphitic carbon carriers, nitrides, silicide, carbides or borides are preferred. The pretreatment mentioned can be an oxidative pretreatment, as described for example in EP-A 848991. Carriers of optionally pretreated activated carbon are preferably used.
Rhenium (Re, als Metall gerechnet) und das weitere Metall der Gruppe VIII oder Ib des Periodensystems sind in einer Menge von jeweils 0,03 bis 30 Gew.-%, bevorzugt 1 bis 12 Gew.-%, besonders bevorzugt 2 bis 5 Gew.-%, bezogen auf den gesamten Katalysator aus Träger und Aktivmasse, aufgebracht.Rhenium (Re, calculated as metal) and the further metal from Group VIII or Ib of the periodic table are in an amount of 0.03 to 30% by weight, preferably 1 to 12% by weight, particularly preferably 2 to 5% by weight .-%, based on the total catalyst from the carrier and active composition, applied.
Es können auf dem Katalysator noch weitere Elemente vorhanden sein. Beispielhaft seien Zn (Zink), Sn (Zinn), Au (Gold), Fe (Eisen), Mn (Mangan), Cr (Chrom), Mo (Molybdän), W (Wolfram) und V (Vanadium) genannt. Ebenso können noch Elemente der Gruppen VII, VIII oder Ib des Periodensystems der Elemente wie Rhenium (Re), Platin (Pt), Ruthenium (Ru), Silber (Ag) und Palladium (Pd) zusätzlich vorhanden sein. Diese Elemente modifizieren den Katalysator im wesentlichen bzgl. Aktivität und Selektivität (Hydrogenolyseprodukte) sind aber nicht essentiell. Ihr Gewichtsverhältnis zu Rhenium kann 0 bis 100, bevorzugt 0,5 bis 30, besonders bevorzugt 0,1 bis 5 betragen. Bevorzugt sind die erfindungsgemäßen Katalysatoren insbesondere chromfrei.There may be other elements on the catalyst. Examples include Zn (zinc), Sn (tin), Au (gold), Fe (iron), Mn (manganese), Cr (chromium), Mo (molybdenum), W (tungsten) and V (vanadium). Likewise, elements of groups VII, VIII or Ib of the periodic table of the elements such as rhenium (Re), platinum (Pt), ruthenium (Ru), silver (Ag) and palladium (Pd) can also be present. These elements modify the catalyst essentially with regard to activity and selectivity (hydrogenolysis products) but are not essential. Their weight ratio to rhenium can be 0 to 100, preferably 0.5 to 30, particularly preferably 0.1 to 5. The catalysts according to the invention are preferably, in particular, free of chromium.
Die Aufbringung der Aktivkomponenten Rhenium und des weiteren Metalls der Gruppe VIII oder Ib des Periodensystems der Elemente kann durch Imprägnierung in einem oder mehreren Schritten mit einer wässrigen, alkoholischen oder mit anderen organischen Lösungsmitteln hergestellten Lösung der jeweiligen gelösten bimetallischen Vorläuferverbindung, besonders bevorzugt des Doppelsalzes der allgemeinen Formel I, Gleichgewichtsadsorption in einem oder mehreren Schritten der in wässriger oder al- koholischer Lösung gelösten bimetallischen Vorläuferverbindung, besonders bevorzugt des Doppelsalzes der allgemeinen Formel I an den Träger vorgenommen werden. Bei diesen Verfahren werden die Aktivkomponenten gleichzeitig und gleichmäßig auf das Trägermaterial aufgebracht werden. Zwischen den einzelnen Imprägnierungs- und Gleichgewichtsadsorptionsschritten liegt jeweils ein Trocknungsschritt zur Entfernung des Lösungsmittels. Bevorzugt geschieht die Aufbringung der Aktivkomponenten durch Imprägnierung mit einer wässrigen Salzlösung in einem Schritt.The application of the active components rhenium and the other metal of group VIII or Ib of the periodic table of the elements can be done by impregnation in one or several steps with an aqueous, alcoholic or other organic solvent solution of the respective dissolved bimetallic precursor compound, particularly preferably the double salt of the general formula I, equilibrium adsorption in one or more steps of the bimetallic precursor compound dissolved in aqueous or alcoholic solution, particularly preferred of the double salt of the general formula I can be carried out on the carrier. With these methods, the active components will be applied simultaneously and evenly to the carrier material. There is a drying step between the individual impregnation and equilibrium adsorption steps to remove the solvent. The active components are preferably applied in one step by impregnation with an aqueous salt solution.
Zur Entfernung des Lösungsmittels nach dem Imprägnierungs- oder Gleichgewichtsadsorptionsschritt erfolgt eine Trocknung des imprägnierten Katalysators. Die Trocknungs-temperatur liegt dabei bei 30 - 350°C, bevorzugt 40 - 280°C, besonders bevorzugt 50 - 150°C.The impregnated catalyst is dried to remove the solvent after the impregnation or equilibrium adsorption step. The drying temperature is 30-350 ° C, preferably 40-280 ° C, particularly preferably 50-150 ° C.
Die Aktivkomponenten sind auf dem Träger des erfindungsgemäßen Katalysators besonders gleichmäßig verteilt, insbesondere weist das Intensitäsverhältnis von Rhenium zum Metall (Me) der Gruppe VIII oder Ib des Periodensystems der Elemente über die gesamten Katalysatorpartikel bei mehr als 99,9 % der analysierten Punkte Schwankungen kleiner als den Faktor 10, bezogen auf den statistischen Mittelwert, bevorzugt bei 98 % der analysierten Punkte auf der Katalysatoroberfläche Schwankungen kleiner als Faktor 5 und besonders bevorzugt in 80 % der analysierten Punkte Schwankungen kleiner als Faktor 2, auf.The active components are particularly evenly distributed on the support of the catalyst according to the invention; in particular, the intensity ratio of rhenium to metal (Me) of Group VIII or Ib of the Periodic Table of the Elements shows less than fluctuations over more than 99.9% of the analyzed points over the entire catalyst particles the factor 10, based on the statistical mean, preferably fluctuations smaller than factor 5 in 98% of the analyzed points on the catalyst surface and particularly preferably fluctuations smaller than factor 2 in 80% of the analyzed points.
Dieser Faktor wurde mit SEM-EDX (Scanning electron microscope-energy dispersive x-ray spectroscopy) bestimmt. Die Methode ist an sich bekannt und beispielsweise in Ulmanns Encylopedia of Industrial Chemistry 6th Edition 2000 Electronic Release be- schrieben.This factor was determined using SEM-EDX (Scanning electron microscope-energy dispersive x-ray spectroscopy). The method is known per se and, for example, in Ulmann's Encyclopedia of Industrial Chemistry 6 th Edition 2000 Electronic Release wrote loading.
Die Katalysatoren werden üblicherweise vor ihrem Einsatz aktiviert. Diese Aktivierung kann durch Anwendung einer reduzierend wirkenden Gasatmosphäre auf den Katalysator geschehen. Bevorzugt wird eine Aktivierung mit Hilfe von Wasserstoff angewen- det. Die Aktivierungs-temperatur liegt dabei üblicherweise bei 100 - 500°C, bevorzugt 130 - 400°C, besonders bevorzugt 150 - 400°C. Alternative Reduktionsmethoden sind die Reduktion der metallischen Komponenten durch in Kontaktbringen mit einem flüssigen Reduktionsmittel wie Hydrazin, Formaldehyd oder Natriumformiat. Dabei werden die flüssigen Reduktionsmittel üblicherweise bei Temperaturen zwischen 10 und 100°C in Kontakt gebracht. Besonders bevorzugt ist das Inkontaktbringen bei Temperaturen zwischen 20 bis 80°C.The catalysts are usually activated before they are used. This activation can be done by applying a reducing gas atmosphere to the catalyst. Activation with the aid of hydrogen is preferably used. The activation temperature is usually 100-500 ° C., preferably 130-400 ° C., particularly preferably 150-400 ° C. Alternative reduction methods are the reduction of the metallic components by bringing them into contact with a liquid reducing agent such as hydrazine, formaldehyde or sodium formate. The liquid reducing agents are usually at temperatures between 10 and 100 ° C. brought into contact. Contacting at temperatures between 20 to 80 ° C. is particularly preferred.
Die Hydrierung wird üblicherweise bei 110 - 250°C, bevorzugt bei 150 - 250°C durch- geführt. Dabei wird üblicherweise bei einem Reaktionsdruck zwischen 5 und 220 bar, bevorzugt 40 und 150 bar hydriert. Die Hydrierung wird in der Flüssigphase bevorzugt im Festbett durchgeführt.The hydrogenation is usually carried out at 110-250 ° C., preferably at 150-250 ° C. Hydrogenation is usually carried out at a reaction pressure between 5 and 220 bar, preferably 40 and 150 bar. The hydrogenation is preferably carried out in the liquid phase in a fixed bed.
Als Ausgangsstoffe für die Hydrierung sind im allgemeinen Carbonylverbindungen ge- eignet, die zusätzlich C-C-Doppel- oder Dreifachbindungen enthalten können. Beispiel für Aldehyde sind Propionaldehyd, Butyraldehyde, Crotonaldehyd, Ethylhexanal, Nonanal und Glucose. Beispiele für Carbonsäuren sind Bernsteinsäure, Fumarsäure, Maleinsäure. Als Ester sind Ester der vorgenannten Säuren, z.B. als Methyl-, Ethyl-, Propyl- oder Butylester zu nennen, ferner sind Lactone, z.B. gamma-Butyrolacton, del- ta-Valerolacton oder Caprolacton einsetzbar. Außerdem können Anhydride wie Bernsteinsäureanhydrid oder Maleinsäureanhydrid verwendet werden. Bevorzugte Ausgangsstoffe sind C -Dicarbonsäuren und/oder deren Derivate, besonders bevorzugt Bernsteinsäure, Maleinsäure, Bernsteinsäureanhydrid, Maleinsäureanhydrid sowie die Ester dieser Säuren. Es können selbstverständlich auch Gemische vorv Alde- hyden, Carbonsäuren, Estern, Anhydriden und/oder Lactonen, bevorzugt Gemische von Carbonsäuren, eingesetzt werden.Suitable starting materials for the hydrogenation are generally carbonyl compounds, which can additionally contain double or triple C-C bonds. Examples of aldehydes are propionaldehyde, butyraldehyde, crotonaldehyde, ethylhexanal, nonanal and glucose. Examples of carboxylic acids are succinic acid, fumaric acid, maleic acid. As esters are esters of the aforementioned acids, e.g. as methyl, ethyl, propyl or butyl esters, lactones, e.g. gamma-butyrolactone, delta-valerolactone or caprolactone can be used. Anhydrides such as succinic anhydride or maleic anhydride can also be used. Preferred starting materials are C -dicarboxylic acids and / or their derivatives, particularly preferably succinic acid, maleic acid, succinic anhydride, maleic anhydride and the esters of these acids. Mixtures of aldehydes, carboxylic acids, esters, anhydrides and / or lactones, preferably mixtures of carboxylic acids, can of course also be used.
Die zu hydrierenden Verbindungen können in Substanz oder in Lösung hydriert werden. Als Lösungsmittel bietet sich z.B. eines der Hydrierprodukte selbst an, oder es werden Stoffe eingesetzt wie Alkohole wie Methanol, Ethanol, Propanol oder Butanol, ferner sind Ether wie THF oder Ethylenglycolether oder gamma-Butyrolacton geeignet. Ein bevorzugtes Lösungsmittel ist Wasser, insbesondere bei der Hydrierung von Carbonsäuren.The compounds to be hydrogenated can be hydrogenated in bulk or in solution. A suitable solvent is e.g. one of the hydrogenation products itself, or substances such as alcohols such as methanol, ethanol, propanol or butanol are used, and ethers such as THF or ethylene glycol ether or gamma-butyrolactone are also suitable. A preferred solvent is water, especially in the hydrogenation of carboxylic acids.
Die Hydrierung kann in der Flüssigphase, ein- oder mehrstufig ausgeübt werden. In der Flüssigphase ist sowohl die Suspensions- als auch die Festbettfahrweise möglich. Bei exothermen Reaktionen kann die Wärme durch außenliegende Kühlmittel abgeführt werden (z.B. Röhrenreaktor). Ferner ist Siedekühlung im Reaktor möglich, vor allem wenn ohne Produktrückführung hydriert werden. Bei Produktrückführung bietet sich ein Kühler im Rückführstrom an.The hydrogenation can be carried out in the liquid phase, in one or more stages. In the liquid phase, both the suspension and the fixed bed procedure are possible. In exothermic reactions, the heat can be dissipated by external coolants (e.g. tubular reactor). Boiling cooling in the reactor is also possible, especially if hydrogenation is carried out without recycling the product. A cooler in the return flow is recommended for product return.
Das erfindungsgemäße Verfahren wird anhand der nachstehenden Beispiele erläutert.The process according to the invention is explained using the examples below.
Beispiele Bestimmung des Intensitätsfaktors mit SEM-EDXExamples Determination of the intensity factor with SEM-EDX
Mit einem SEM-EDX Spektrometer des Typs Philips ESEM-XL30-FG mit EDX-Sonde wurden die Intensitäten (entsprechend den Gehalten) des Rheniums und des Palladiums bestimmt. Die Analysenspannung betrug 30 KV. Die Partikel wurden zur Vorbereitung so geteilt, dass eine saubere Schnittfläche erhalten wurde. Von dieser Schnittfläche wurden mehr als 300 μm in Schritten zu je 15 μm mit SEM-EDX auf ihren Gehalt an Pd und Re untersucht. An jedem Messpunkt kann ein Verhältnis der Intensitäten von Pd und Re berechnet werden.The intensities (corresponding to the contents) of the rhenium and the palladium were determined using a Philips ESEM-XL30-FG SEM-EDX spectrometer with EDX probe. The analysis voltage was 30 KV. The particles were divided in preparation so that a clean cut surface was obtained. From this cut surface, more than 300 μm in steps of 15 μm were examined with SEM-EDX for their Pd and Re content. A ratio of the intensities of Pd and Re can be calculated at each measuring point.
Beispiel 1example 1
15,83 g Pd(NO3)2 wurden mit 8 g 25%iger NH3-Lösung versetzt und mit einer Lösung von 8,66 g NH4ReO4 in 98 g Wasser vermischt. Die Verbindung Pd(NO3)2 (ReO4)2 kris- tallisierte aus. Das durch Filtration gewonnene Produkt wurde mit Wasser gewaschen und getrocknet.15.83 g of Pd (NO 3 ) 2 were mixed with 8 g of 25% NH 3 solution and mixed with a solution of 8.66 g of NH 4 ReO 4 in 98 g of water. The compound Pd (NO 3 ) 2 (ReO 4 ) 2 crystallized out. The product obtained by filtration was washed with water and dried.
Beispiel 2: Katalysator AExample 2: Catalyst A
1 ,11 g des Pd-Re-Salzes, hergestellt nach Beispiel 1 , wurden bei 80°C in 20 g Wasser gelöst. 30 g eines Aktivkohleträger (Degussa 180 der Firma Degussa AG, Düsseldorf) wurden mit der Lösung des Pd-Re-Salzes bei 70°C getränkt. Sodann wurde der Katalysator bei 120°C in 100 Nl/h Stickstoff (N2) getrocknet. Anschießend wurde 30 min bei gleicher Temperatur und 30 min. bei 200°C mit 0,5 % Wasserstoff (H2) enthaltendem N2 (100 Nl/h) reduziert. Dann wurde für 1 h die Wasserstoff menge auf 5 % und für weitere zwei Stunden auf 100 % erhöht. Danach wurde die Temperatur auf 400°C sowie der Fluss auf 3000 l/h H2 erhöht. Die Heizraten betrugen dabei jeweils 5°C/min. Abschließend wurde der Katalysator nach Abkühlen in N2 bei Raumtemperatur 7 h in 5 % Luft in N2 passiviert. Der Katalysator enthielt 0,5 Gew.-% Pd und 2 Gew.-% Re.1.11 g of the Pd-Re salt, prepared according to Example 1, were dissolved in 20 g of water at 80.degree. 30 g of an activated carbon carrier (Degussa 180 from Degussa AG, Dusseldorf) were soaked at 70 ° C. with the solution of the Pd-Re salt. The catalyst was then dried at 120 ° C. in 100 Nl / h nitrogen (N 2 ). Then was 30 min at the same temperature and 30 min. at 200 ° C with 0.5% hydrogen (H 2 ) containing N 2 (100 Nl / h) reduced. The amount of hydrogen was then increased to 5% for 1 h and to 100% for a further two hours. The temperature was then increased to 400 ° C. and the flow to 3000 l / h H 2 . The heating rates were 5 ° C / min. Finally, after cooling in N 2 at room temperature, the catalyst was passivated in 5% air in N 2 for 7 h. The catalyst contained 0.5 wt% Pd and 2 wt% Re.
Beispiel 3Example 3
1 ,11 g des Pd-Re-Salzes wurden in 130 g Wasser bei 40°C gelöst. 10 g dieser Lösung wurden unter Rühren auf 30 g des Aktivkohleträgers (Degussa 180) aufgebracht. So- dann wurde der Katalysator 1 h bei 120°C getrocknet. Nach einem Waschschritt mit Wasser wurde die Tränk- und Trockenprozedur wiederholt bis die ganze Lösung auf den Träger aufgebracht war. Anschließend wurde der Katalysator getrocknet und analog Beispiel 2 reduziert. Der Katalysator enthielt 0,5 Gew.-% Pd und 2 Gew.-% Re. Beispiel 41.11 g of the Pd-Re salt were dissolved in 130 g of water at 40.degree. 10 g of this solution were applied to 30 g of the activated carbon carrier (Degussa 180) with stirring. Then the catalyst was dried at 120 ° C. for 1 h. After a washing step with water, the soaking and drying procedure was repeated until all of the solution had been applied to the support. The catalyst was then dried and reduced as in Example 2. The catalyst contained 0.5 wt% Pd and 2 wt% Re. Example 4
20 g des Katalysators A wurden in einen Rohrreaktor eingefüllt und bei Atmosphärendruck und 150°C 2 h lang mit N2 gespült (240 Nl/h). Anschließend wurden 5 % H2 zu- gemischt und nach zwei Stunden die Temperatur auf 200°C erhöht und über Nacht gehalten. Nach Umschalten auf eine 50 %ige H2-N2-Mischung wurde die Temperatur für 1 h auf 230°C erhöht und schließlich wurde eine weitere Stunde in 120 Nl/h reinem H2 reduziert. Abschließend wurde der Druck auf 40 bar erhöht. Mit diesem aktivierten Katalysator A wurde Bernsteinsäureanhydrid (BSA), das in einer Menge von 6.06 g/h als 20 gew.-%ige Lösung in gamma-Butyrolacton zudosiert wurde, bei 235°C und 40 bar in kontinuierlichen Betrieb hydriert. Das Molverhältnis H2:BSA betrug 35. Es wurde bei einem Umsatz von 91 % eine Produktausbeute 81 % (39 % Tetrahydrofuran (THF) und 35 % γ-Butyrolacton) erzielt.20 g of catalyst A were introduced into a tubular reactor and flushed with N 2 (240 Nl / h) at atmospheric pressure and 150 ° C. for 2 h. 5% H 2 were then mixed in and after two hours the temperature was raised to 200 ° C. and held overnight. After switching to a 50% H 2 -N 2 mixture, the temperature was raised to 230 ° C. for 1 h and was finally reduced for a further hour in 120 Nl / h of pure H 2 . Finally, the pressure was increased to 40 bar. With this activated catalyst A, succinic anhydride (BSA), which was metered in at 6.06 g / h as a 20% strength by weight solution in gamma-butyrolactone, was hydrogenated at 235 ° C. and 40 bar in continuous operation. The molar ratio H 2 : BSA was 35. With a conversion of 91%, a product yield of 81% (39% tetrahydrofuran (THF) and 35% γ-butyrolactone) was achieved.
Vergleichsbeispiel 1 : Katalysator V1Comparative Example 1: Catalyst V1
60 g eines mit Wasser vorbefeuchteten Aktivkohleträgers (Degussa 180) wurde unter Rühren mit einer Lösung enthaltend 0,78 g Pd (NO3)2 2H2O und 1 ,52 g HReO4 (72,8 gew.-%ige Lösung) in 20 ml Wasser bei Raumtemperatur getränkt. Anschlie- ßend wurde der Katalysator analog der für Katalysator A in Beispiel 2 beschriebenen Trocknung und Reduktion behandelt. Der Katalysator enthielt 0,5 Gew.-% Palladium und 2 Gew.-% Rhenium.60 g of an activated carbon carrier pre-moistened with water (Degussa 180) was stirred in with a solution containing 0.78 g of Pd (NO 3 ) 2 2H 2 O and 1.52 g of HReO 4 (72.8% by weight solution) 20 ml of water soaked at room temperature. The catalyst was then treated analogously to the drying and reduction described for catalyst A in example 2. The catalyst contained 0.5% by weight of palladium and 2% by weight of rhenium.
Vergleichsbeispiel 2:Comparative Example 2:
20g des Katalysators V1 wurden analog Beispiel in einen Rohrreaktor eingebaut und analog Beispiel 5 aktiviert. Mit diesem aktivierten Katalysator A wurde Bernsteinsäureanhydrid (BSA), das in einer Menge von 5,94 g/h als 20 gew.-% Lösung in gamma- Butyrolacton zudosiert wurde, bei 235°C und 40 bar im kontinuierlichen Betrieb hyd- riert. Das Molverhältnis H2:BSA betrug 35. Es wurde bei einem Umsatz von 80 % eine Produktausbeute von 77 % (9 % Tetrahydrofuran (THF) und 53 % γ-Butyrolacton). 20 g of the catalyst V1 were installed in a tubular reactor as in the example and activated in the same way as in the example 5. With this activated catalyst A, succinic anhydride (BSA), which was metered in at 5.94 g / h as a 20% by weight solution in gamma-butyrolactone, was hydrogenated at 235 ° C. and 40 bar in continuous operation. The molar ratio H 2 : BSA was 35. With a conversion of 80%, the product was 77% (9% tetrahydrofuran (THF) and 53% γ-butyrolactone).

Claims

Patentansprüche claims
1. Rheniumhaltiger Trägerkatalysator, dadurch gekennzeichnet, dass Rhenium und mindestens ein weiteres Metall der Gruppen VIII oder Ib des Periodensystems der Elemente, insbesondere Ruthenium (Ru), Rhodium (Rh), Palladium (Pd),1. rhenium-containing supported catalyst, characterized in that rhenium and at least one other metal from groups VIII or Ib of the Periodic Table of the Elements, in particular ruthenium (Ru), rhodium (Rh), palladium (Pd),
Osmium (Os), Iridium (Ir), Platin (Pt), Kupfer (Cu), Silber (Ag) oder Cobalt (Co) in Form mindestens einer bimetallischen Vorläuferverbindung auf den Träger aufgebracht wird.Osmium (Os), iridium (Ir), platinum (Pt), copper (Cu), silver (Ag) or cobalt (Co) in the form of at least one bimetallic precursor compound is applied to the carrier.
2. Rheniumhaltiger Trägerkatalysator nach Anspruch 1 , dadurch gekennzeichnet, dass als bimetallische Vorläuferverbindung Perrhenat-Doppelsalze eingesetzt werden.2. Rhenium-containing supported catalyst according to claim 1, characterized in that perrhenate double salts are used as the bimetallic precursor compound.
3. Rheniumhaltiger Trägerkatalysator nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass ein Doppelsalz der allgemeinen Formel (I)3. Rhenium-containing supported catalyst according to claim 1 or 2, characterized in that a double salt of the general formula (I)
[Mea (NH3)b (OH)J (ReO4)d • eH2O (I)[Me a (NH 3 ) b (OH) J (ReO 4 ) d • eH 2 O (I)
eingesetzt wird, wobei Me für ein Metall der Gruppen VIII und Ib des Periodensystems der Elemente, insbesondere für Ru, Rh, Pd, Os, Ir, Pt, Cu, Ni,is used, where Me for a metal from groups VIII and Ib of the Periodic Table of the Elements, in particular for Ru, Rh, Pd, Os, Ir, Pt, Cu, Ni,
Ag oder Co steht, a 1 oder 2 bedeutet, b eine ganze Zahl von 1 bis 8, c eine ganze Zahl von 0 bis 5, d 2, 3 oder 4 und e eine ganze Zahl von 0 bis 12 darstellt.Ag or Co is, a is 1 or 2, b is an integer from 1 to 8, c is an integer from 0 to 5, d 2, 3 or 4 and e is an integer from 0 to 12.
4. Rheniumhaltige Trägerkatalysatoren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass als bimetallische Vorläuferverbindung Pd (NH3) (ReO4)2 und/oder Pt (NH3)4 (ReO )2 eingesetzt wird.4. Rhenium-containing supported catalysts according to one of claims 1 to 3, characterized in that Pd (NH 3 ) (ReO 4 ) 2 and / or Pt (NH 3 ) 4 (ReO) 2 is used as the bimetallic precursor compound.
5. Rheniumhaltige Trägerkatalysatoren, nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass Rhenium und das weitere Metall der Gruppe VIII oder Ib des Periodensystems der Elemente in einer Menge von jeweils 0,03 bis 30 Gew.-%, bezogen auf den gesamten Katalysator, vorhanden sind.5. rhenium-containing supported catalysts, according to one of claims 1 to 4, characterized in that rhenium and the further metal of group VIII or Ib of the periodic table of the elements in an amount of 0.03 to 30 wt .-%, based on the total Catalyst, are present.
6. Rheniumhaltige Trägerkatalysatoren, nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das elektronenmikroskopisch bestimmte6. rhenium-containing supported catalysts, according to one of claims 1 to 5, characterized in that the electron microscope determined
Verhältnis von Rhenium zum Metall (Me) der Gruppe VIII oder Ib des Periodensystems der Elemente über den gesamten Katalysatorpartikel in 98 % der analysierten Punkte keine Schwankungen um einen Faktor kleiner 5 aufweist. Ratio of rhenium to metal (Me) of group VIII or Ib of the periodic table of the elements over the entire catalyst particles in 98% of the analyzed points shows no fluctuations by a factor of less than 5.
7. Verfahren zur Herstellung von Gemischen aus Tetrahydrofuran und gamma- Butyrolacton durch katalytische Hydrierung von Carbonylverbindungen, dadurch gekennzeichnet, dass ein Katalysator nach einem der Ansprüche 1 bis 6 verwendet wird.7. A process for the preparation of mixtures of tetrahydrofuran and gamma-butyrolactone by catalytic hydrogenation of carbonyl compounds, characterized in that a catalyst according to one of claims 1 to 6 is used.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass die Carbonylverbindung ausgewählt ist aus Aldehyden, Carbonsäuren, Estern, Anhydriden und/oder Lactonen.8. The method according to claim 7, characterized in that the carbonyl compound is selected from aldehydes, carboxylic acids, esters, anhydrides and / or lactones.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass die9. The method according to claim 8, characterized in that the
Carbonylverbindung ausgewählt ist aus Maleinsäure, Fumarsäure, Bernsteinsäure oder Estern oder Anhydriden davon.Carbonyl compound is selected from maleic acid, fumaric acid, succinic acid or esters or anhydrides thereof.
10. Verfahren nach einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass die Hydrierung ist der Flüssigphase an fest angeordneten Katalysatoren bei einem10. The method according to any one of claims 7 to 9, characterized in that the hydrogenation is the liquid phase on fixed catalysts in a
Druck im Bereich von 5 bis 220 bar und einer Temperatur im Bereich von 110 bis 250°C durchgeführt wird. Pressure in the range of 5 to 220 bar and a temperature in the range of 110 to 250 ° C is carried out.
PCT/EP2003/012379 2002-11-11 2003-11-06 Supported catalyst containing rhenium and method for hydrogenation of carbonyl compounds in liquid phase by means of said catalyst WO2004043592A1 (en)

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AU2003276258A AU2003276258A1 (en) 2002-11-11 2003-11-06 Supported catalyst containing rhenium and method for hydrogenation of carbonyl compounds in liquid phase by means of said catalyst
EP03810970A EP1572354B1 (en) 2002-11-11 2003-11-06 Supported catalyst containing rhenium and method for hydrogenation of carbonyl compounds in liquid phase by means of said catalyst
US10/534,621 US7214641B2 (en) 2002-11-11 2003-11-06 Catalyst and hydrogenation of carbonyl compounds in the liquid phase using the catalyst
DE50303747T DE50303747D1 (en) 2002-11-11 2003-11-06 RHENIUM-CONTAINING SUPPORT CATALYST AND METHOD FOR HYDROGENATING CARBONYL COMPOUNDS IN A LIQUID PHASE USING THE CATALYST
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